Chemical products and process of preparing same



Patented Aug. 6, 1946 CHEMICAL PRQDUCTS AND PROCESS OF PREPARING John C. Zimmer, Union, and Arnold J. Morway, Clark Township, Union County, N. J assignors to Standard Oil Development Company, a corporation of Delaware No Drawing. Application September 27, 1941', Serial No. 412,596

1 Claim.

This invention deals essentially with extreme pressure lubricants adapted for carrying much higher loads than can be carried safely by the usual unblended lubricants. More specifically, it involves the use of certain phosphorus, sulfur and halogen containing compounds for improving the load carrying capacity of ordinary lubricants such as mineral lubricating oils.

A number of phosphorus compounds and derivatives thereof have been suggested in the art for use as extreme pressure lubricating agents. These products, however, involve the formation of considerable amounts of sludge during their manufacture or, if prepared from phosphor-us halides, they may contain f-ree hydrochloric acid which is corrosive to steel. -Most of them also possess only weak pressure-resisting properties, thereby involving danger of-scoring of the hypoid gears or other moving parts lubricated thereby.

One purpose of this invention is to avoid these prior art difiiculties ,by producing a substantially non-corrosive extreme pressure agent without excessivesludge-formation capable of carrying high loads and retaining its stability over a long period of time.

According to the invention, a halogenated aliphatic, aromatic-or terpene compound, especially one of; at least 8-10 carbon atoms, preferably more than '15 carbon atoms, e. g., a chlorinated hydrocarbon such as chlorinated parafi'in or petrolatum wax, other chlorinated petroleum fractions, e. g. naphtha, kerosene, or light lubricatingoils, etc., or similar material containing at least or 10% chlorine is reacted with 1-10% phosphorus sesquisulfide (P483) at about 300-400 F. until reaction is substantially complete. Although halogenated hydrocarbon materials are preferred in the above reaction, because they result in products which are more soluble and more stable in mineral lubricating oils, one may also, under some circumstances, use halogenated fatty acids or esters such as chlor-stearicacid or chlorethyl stearate or chlorinated alcohol or ether. Other phosphorus sulfides are not as effective as P sa since they'tend, to produc c ssi e slud lng and do not give products-as rich in phosphorus and sulfur. The product thus prepared may be neutralized if desired to remove any ex,- cess halogen halideliberated by the reaction, and then blended in the lubricating base stock in amounts-of l-to 10%, more or less.

In the preferred embodiment, chlorinated par-- afiin wax containin about -40%, or preferably about C1 is heated to 300-400" F. With 2-5% P ss, producing a reaction product containin 27% G1, 1.5% S, and 1.0% P. This may then be blended in 5% concentration with 85% untreated mineral oil and 10% sulfurized fatty oil, especially a non-corrosive sulfurized oil of the type of sperm oil or sulfurized fatty alcohols, such as cetyl alcohol, degras alcohols (e. g. wool fat) to produce a highly suitable extreme-pressure lubricant for hypoid lubrication, production of cutting oils (soluble or non-aqueous), and in general, for uses requirin a lubricant capable of withstanding high load and pressures. Another raw material for the preparation of the blending agent previously described is the by-product overhead slop cut from the manufacture of a pour depressor by the Friedel-Crafts condensation or chlorinated paraffin wax with naphthalene, according to the Davis Patent 1,815,022. This slop out, which essentially contains unreacted Wax, naphthalene, simple alkylated naphthalenes, alkylated naphthalenes, etc., is chlorinated to the extent of about 20 or 30% Cl before it is reacted with the P483. The composition of such a slop cut is approximately:

20-30% unreacted wax 70-60% alkylated naphthalene Trace wax olefines Balance naphthalene (M. P.+40 F.)

The chlorination of the paraffin wax slop out or other starting material is preferably carried out under the following conditions:

Chlorine gas is passed through a sintered glass disk (or other suitable. porous gas-dispersing means) int the wax at ambient temperatures with an immediate rise in temperature as the chlorine is combined with the wax. The temperature is maintained between and 200 F. by controlling the flow of chlorine. Under these conditions an increase in weight of the starting material of approximately 30% is obtained in about 6 hours. When a higher melting point wax is used than slop Wax, the starting temperature may be increased to the melting point of the wax, holding the chlorination temperature in the same range. The product is a clear, dark red liquid.

It is essential that a halogenated compound be reacted with the P433, since ordinary mineral or fatty oils or other compounds devoid of halogen, outside of giving excessive sludging, show very little reaction with P483 to give a satisfactoryyield of an oil soluble phosphorus and sulfur-containing product of satisfactory E. P. propertiesr The products produced according to the present i nt n a also been found suitable 3. as lubricant anti-oxidants and bearing corrosion inhibitors when employed in small amounts, in the neighborhood of 0.1%.

An alternative method which is also satisfactory but not as convenient as the one just outlined, is to react a fatty or mineral oil or synthetic oil simultaneously with chlorine and a sulfide of phosphorus, e. g. P4S3, PzSs, P253, PSC13, or mixtures of phosphorus and sulfur.

If the chlorinated compound is treated with 3% or less of the phosphorus sulfide in a finely divided state at 250 to 370 asatisfactory product is obtained. Excessive heating, especially at higher temperatures, should be avoided, since it is conducive to coking and formation of a less active and stable product. With larger amount sof phosphorus sulfide, higher temperatures and longer periods of treating are necessary. At about 250 F., copious white fumes are liberated, indicating that reaction temperature is reached, and as the heating progresses, some glowing may occur. After the material has cooled, the product containing chlorine, sulfur and phosphorus is dissolved in ordinary lubri cating oils, with or without the addition of other blending agents.

The following examples illustrate some of the many phases involved in this invention:

Example 1 A wax-naphthalene condensation product slop cut was chlorinated to about 30% chlorine and treated with phosphorus sesquisulfide as outlined above. In the P483 treatment, 3.0% P4S3 were added in finely divided state and reacted with the chlorinated slop wax at 250-300 F. When the P4S3 was completely dissolved, white fumes came over and a small amount of glow occurred; after about 15 minutes at 300 F., the reaction was completed. The product was liquid; The product was then dissolved in 10% concentration to a Pennsylvania gear lubricating oil of 200 seconds Saybolt viscosity at 210 F. The resulting blend carried a load of 15,000 lbs. in the Almen test, with low friction (35) and perfect pin condition. In the S. A. E. machine test, the blend carried a load corresponding to 390 lbs. scale reading at 1000 R. P. M. with a 14.6:1 loading ratio. In the copper strip corrosion test, the blend showed only a slight bronzing of the copper strip after 3 hrs. immersion at 210 F.

Example 2 ing oil in 5% concentration, and this blend passed the Almen test of 15,000 lbs. (gradual loading), and 13,000 lbs. (shock loading), with excellent pin condition and low frictional readings. These results are surprisingly good compared to the plain oil which only carries 3,000 lbs. on the Almen machine, both by gradual and shock load- Two parts of P483 reacted with 20 parts of chlorinated slop wax, same material as used in Example 1 (containing 30% chlorine), were About 10% of P483 (20 g.) was added to sperm oil (200 g.) in a dispersion. While mixing the suspension, chlorine gas, sufiicient to react completely with the P4s3, was passed through the suspension for about 30 minutes, during which time the temperature rose from about 80 F. to

about 100-150" F. After the reaction mixture became clear, a stream of air was blown through the product to remove any free HCl. Afterjair' blowing, the product was dissolved in a lubricat- During the introduction of the chlorine through the P483 suspension in sperm oil, some PCl5 was formed which condensed on the sides of the flask. This material may be removed and replaced in the sperm oil, if desired. No sludge is formed during this reaction if P4s3 is employed, although this is not the case if PzSa of P2Ss or other phosphorus compounds are cooked into fatty or mineral oils.

Example 4 10 grams of P4Sa were suspended in 200 grams of a naphthenic type oil having 40 seconds Saybolt viscosity at 210 F. Chlorine wa's'added ata very slow rate with a temperature rise to 175 F. Chlorine was continuously passed through the suspension until all P433 was completely reacted and in solution. A 5% by weight solution of the resulting product in a naphthenic oil of 40 seconds Saybolt viscosity at210 F..carried 14,000 lbs. on the Almen machine, gradual loading.

' Example 5 About 98 parts of 118-120 F. melting point per:

afiin wax was chlorinated to about 40% chlorine content and reacted with 2 parts of P483 at 370. The reaction prodfurized sperm oil, the final blend having the following composition:

Paraffinic 01 naphthenic basemineral ear oil seconds viscosity at 0 R) a; V

blend imparted a very slight bronzing to a QODPcr strip in the coppers'trip corrosion test at 210? F. On the S. A.-E. machine test it carrieda load of 320-340 lbs. scale reading at 1000 R. P ll/Land 14.6:1 loading ratio. The mineral oil base stock used in this corrosion and load carrying test was the same as used in Example 1. (It showed a'scale reading of '70 lbs. under "similar test conditions.) A blend of the mineral oil and the sulfurized sperm oil, but not contain ing the Ch1OI'WaX-P4s3 reaction product, showeda corresponding scale readingjof '210 1bs., thus indicating that the chlorwax-PrSz reaction protl uct resulted in a very substantial andunexpected. improvement in the extreme pressure lubricating property, without any substantial increase in corrosive tendencies.

, Example 6 Seven parts of chlorinated wax having a 40% chlorine content were blended with 10 parts of a non-corrosive sulfurizecl 'spern'roil. This mixture wa s-then reacted at 250-370 F. with 0.15 part of Pisa. This cleandark redproduct was compounded with 83 parts of mineral gear oil to give a clear, non-sludging extreme pressure lubricant. "Alubricant prepared by thisrnethod, carried 15,000 lbs. gradual and shockloading onjthe Almen'machinetest'at 600 R P withexcellent pin conditions, and on the S. A. E. machine test carried a load corresponding to 340 lbs scale reading at 1000 R. P. M. and 14.6:1 loading ratio. On the copper strip corrosion test (3 hrs. at 210 F.) only a slight bronzing of the copper strip was encountered.

This shows that the primary advantageous features of the present invention are not prevented from having their beneficial eifect if the sulfurized sperm oil is added to the chlorinated wax before reaction of the latter with P483.

Example 7 About 98 parts of melted 118-120 F. melting point parafiin wax were mixed with 2 parts of P483. In a suitable apparatus, chlorine gas was passed through the mixture at 150-200 F. until the mixture had been chlorinated to approximately 40% chlorine content. This material was air-blown to remove any entrapped hydrochloric acid gas. After air blowing until no appreciable sharp odor was noticed in the product, the clear, yellow, syrupy product was blended with a noncorrosive sulfurized fatty oil and mineral oil to give the following composition:

7% of the above reaction product. 10% non-corrosive sperm fatty oil. 83% mineral gear oil (90 vis. Saybolt at 210 F).

This blend, when tested on the S. A. E. machine test, carried a load corresponding to 325/350 scale pull at 1000 R. P. M. and 4.6: 1 loading ratio. On the copper strip corrosion test (heating 3 hrs. at 210 F.) and the General Motors steel corrosion test (heating '75 parts of the lubricant and 25 parts of water for 18 hours at 200 F. in contact with a steel rod) only a very slight bronzing of the copper and no discoloration of the steel rod was effected.

The mineral oil base stock and the blend of the latter with sulfurized sperm oil, used in this test, were the same as described in Example 4.

Other materials such as polymer thickeners or V. I. improvers, soluble metal soaps (e. g. aluminum, zinc or lead naphthenate, calcium stearate or phenyl stearate, etc.) anti-oxidants, dyes, pour inhibitors, resins, voltolized mineral and/or fatty oils, fatty or mineral residua, or pitches, phosphorus esters, oiliness agents, sulfurized terpenes, sulfurized mineral oils and extracts, sulfur compounds occurring in petroleum or syn thetically prepared sulfur compounds, especially those having a low volatility and freedom of odor, and the like, may be added to these compositions.

The compounds produced according to this invention may also be added to grease, industrial oils and lubricants, Diesel fuels, slushing oils, and

the like.

This application is a continuation-in-part of application Serial No. 272,594, filed May 9, 1939, now Patent 2,307,183, issued January 5, 1943.

It is not intended that the invention be limited to any of the materials which have been mentioned merely as specific examples, nor by the specific proportions given for the sake of illustration, nor by any theory as to the mechanism of the invention.

We claim:

The process which consists in treating parafiin Wax with chlorine until it contains about 30%-40% by weight of chlorine, and reacting the resultant chlorinated paraffin waxwith about 2%-5% by weight of phosphorus sesquisulfide at a temperature of about 250-370 F.

JOHN C. ZIMMER. ARNOLD J. MORWAY. 

